energies

Article
Polymer Injectivity: Investigation of Mechanical
Degradation of Enhanced Oil Recovery Polymers
Using In-Situ Rheology
Badar Al-Shakry 1,2, * , Tormod Skauge 3 , Behruz Shaker Shiran 2 and Arne Skauge 1,2,3
1 Department of Chemistry, University of Bergen, Allegaten 41, 5007 Bergen, Norway; Arne.Skauge@uib.no
2 NORCE Energy, CIPR, Nygårdsgaten 112, 5008 Bergen, Norway; besh@norceresearch.no
3 Energy Research Norway, Allegaten 41, 5007 Bergen, Norway; Tormod.Skauge@energyresearch.no
* Correspondence: Badar.Al-Shakry@uib.no; Tel.: +47-5558-3672




Received: 22 November 2018; Accepted: 19 December 2018; Published: 24 December 2018


Abstract: Water soluble polymers have attracted increasing interest in enhanced oil recovery (EOR)
processes, especially polymer flooding. Despite the fact that the flow of polymer in porous medium
has been a research subject for many decades with numerous publications, there are still some research
areas that need progress. The prediction of polymer injectivity remains elusive. Polymers with similar
shear viscosity might have different in-situ rheological behaviors and may be exposed to different
degrees of mechanical degradation. Hence, determining polymer in-situ rheological behavior is of
great significance for defining its utility. In this study, an investigation of rheological properties and
mechanical degradation of different partially hydrolyzed polyacrylamide (HPAM) polymers was
performed using Bentheimer sandstone outcrop cores. The results show that HPAM in-situ rheology is
different from bulk rheology measured by a rheometer. Specifically, shear thickening behavior occurs
at high rates, and near-Newtonian behavior is measured at low rates in porous media. This deviates
strongly from the rheometer measurements. Polymer molecular weight and concentration influence
its viscoelasticity and subsequently its flow characteristics in porous media. Exposure to mechanical
degradation by flow at high rate through porous media leads to significant reduction in shear
thickening and thereby improved injectivity. More importantly, the degraded polymer maintained
in-situ viscosity at low flow rates indicating that improved injectivity can be achieved without
compromising viscosity at reservoir flow rates. This is explained by a reduction in viscoelasticity.
Mechanical degradation also leads to reduced residual resistance factor (RRF), especially for high
polymer concentrations. For some of the polymer injections, successive degradation (increased
degradation with transport length in porous media) was observed. The results presented here may
be used to optimize polymer injectivity.

Keywords: enhanced oil recovery (EOR); polymer flooding; injectivity; rheology; viscoelasticity;
non-Newtonian flow; mechanical degradation; HPAM

1. Introduction
In today’s oil industry, chemical enhanced oil recovery techniques such as polymer flooding
play a substantial role in promoting oil production. This is attributed to the achieved improvement
on sweep efficiency that boosts oil production over conventional waterflooding. In such a process,
water-soluble polymers are added to viscosify injected water in order to achieve lower viscosity
contrast between injected water and displaced oil, and therefore a favorable mobility ratio [1]. Besides
mobility control, high viscosity polymers are required for better conformance control relevant to
heterogeneous reservoirs with high permeability variations such as the presence of thief zones [2].

Energies 2019, 12, 49; doi:10.3390/en12010049 www.mdpi.com/journal/energies

Energies 2019, 12, 49 2 of 25

There are two types of polymers suit enhanced oil recovery (EOR) applications which are: biopolymers,
e.g., xanthan, and synthetic polymers, e.g., partially hydrolyzed polyacrylamide (HPAM). Regardless
of the nature and differences in the molecular structure of these two polymers, polymer viscosity is the
main physical property in the context of polymer flooding. Polymer viscosity depends on polymer
molecular structure, molecular weight [3], polymer concentration [4], salinity [5,6], temperature [7,8],
degree of hydrolysis [9], pH [10], flow model and type of forces dominating the flow [11].
While xanthan is well-known to be viscous dominated, HPAM is strongly influenced by both
viscous and elastic properties [12]. It is essential to understand the significance and consequences
when HPAM fluids become elastic dominated. HPAM viscoelasticity is important for many
applications in the oil industry in general (e.g., drag reduction, drilling, etc.) and specifically in
EOR applications such as polymer flooding [1,13–16], Low Salinity Polymer (LSP) flooding [17,18]
and Alkaline-Surfactant-Polymer (ASP) flooding [19,20]. In polymer flooding, HPAM viscoelasticity is
believed to contribute to higher oil recovery in general and some claim that it might reduce residual
oil saturation due to promoting pulling effect mechanisms [21–24]. HPAM shear thickening behavior
may, in some cases, contribute to improving front stability and oil recovery [25]. On the other hand,
the significant pressure gradient associated with shear thickening phenomena can limit polymer
injection, cause wellbore damage or fracturing. The influence of mechanical degradation on shear
rheology will be discussed in this paper.

Polymer Injectivity and Mechanical Degradation

Polymer injectivity is a measure of how easily a polymer solution can be delivered into a reservoir
formation [26]. It is also a measure of how fast polymer solution can be injected and propagate through
the reservoir. It is a critical task because a decline in injectivity can turn the predicted cashflow of
polymer flooding projects negatively [27,28]. This is basically due to the delay of oil production or
high pumping cost. Both aforementioned polymers (xanthan and HPAM) may suffer from injectivity
problems for different reasons. For instance, the presence of microgels and impurities in xanthan may
limit its injectivity [29]. However, HPAM viscoelasticity and retention are the main factors that restrict
its injectivity. The design of polymer flooding projects has to cover some key aspects such as reservoir
formation, oil saturation, injection strategy, polymer rheology, degradation, compatibility with other
chemicals, economy, etc. [30]. This paper intends to investigate some of these aspects such as the link
between polymer rheology and degradation.
The theories and observations associated with the characterization of flow of biopolymers such as
xanthan are typically united in that xanthan has pseudoplastic rheological behavior in porous media
similar to that predicted in pure shear flow such in the rheometer [31–35]. However, the situation
is more complicated for HPAM due to its viscoelastic nature and the complexity of porous media.
Despite the rich literature of polymer flow in porous media, the theoretical interpretations are still
conflicting on the analysis of the observed HPAM in-situ flow behaviors. HPAM polymers are
well-known to have high polydispersity index [36] and possess long relaxation time. HPAM has
a flexible molecular structure and highly sensitive to shear environments. When HPAM flows
in porous media, it is exposed to both shear and elongational deformations as it is transported
through converging-diverging (C↔D) flow channels [36,37]. This results in successive expansion and
contraction (E↔C) of polymer conformation as it flows through porous media. Figure 1 illustrates
a schematic representation of typical flow regions that are exhibited by HPAM with respect to shear
rate. The polymer exhibits near-Newtonian behavior at which its apparent viscosity is independent of
. .
imposed shear rates (γ < γc1 ). As the shear rate increases further, apparent viscosity decreases and the
polymer solution exhibits shear thinning behavior. During shear thinning, polymer molecules start to
disentangle with increasing shear rate until approaching another Newtonian plateau at which the state
.
of disentanglement is very high. However, above γc2 , the extensional flow becomes predominant
at which polymer chains have insufficient time to recoil and align with the flow causing coil-stretch
(C↔S) transition that yields in a gradual increase of apparent viscosity with shear rate. The normal
Energies 2019, 12, 49 3 of 25

stresses that are responsible for chain stretch cause a rise in the extensional viscosity and consequently
Energies 2018, 11, x FOR PEER REVIEW 3 of 25
cause pressure buildup and high apparent viscosity (shear thickening behavior). If the stretch rates that
are associated
stretch with
rates that areshear thickening
associated with behavior are highbehavior
shear thickening enough, chain stretch
are high might
enough, evolve
chain intomight
stretch chain
fragmentation. Chain scissions due to mechanical degradation yields in viscosity
evolve into chain fragmentation. Chain scissions due to mechanical degradation yields in viscosity loss as can be seen
at high shear rates displayed in Figure 1. These flow phenomena are detailed
loss as can be seen at high shear rates displayed in Figure 1. These flow phenomena are detailed elsewhere [11,37–40].
The large strain
elsewhere forcesThe
[11,37–40]. cause large
large molecules
strain to shear
forces cause preferentially.
large molecules to Literature reviews onLiterature
shear preferentially. polymer
mechanical degradation [41,42] showed that the assessment of mechanical
reviews on polymer mechanical degradation [41,42] showed that the assessment of mechanical degradation is complex,
particularly
degradation inisthecomplex,
presence particularly
of entanglements andpresence
in the concentrated conformational regimes.
of entanglements It is very
and concentrated
important to understand how HPAM macromolecules contribute to changing
conformational regimes. It is very important to understand how HPAM macromolecules contribute its flow phenomena and
increasing its apparent viscosity at high flow rates that scales several folds higher
to changing its flow phenomena and increasing its apparent viscosity at high flow rates that scales than predicted in
simple
several shear
folds flow
higher such
thanthat generated
predicted by the rheometer.
in simple shear flow such that generated by the rheometer.

Figure 1.
1 Schematic
Schematicdiagram
diagram of
of HPAM
HPAM apparent viscosity vs shear rate.

In addition to HPAM shear shear stability

stability discussed
discussed above,
above, the dimensions and conformation of
HPAM molecules strongly depend on the salt concentration and types types of TDS existing
existing inin solution.
solution.
HPAM is is aanegatively
negativelycharged
chargedpolymer,
polymer, and therefore at the presence of salts, the
and therefore at the presence of salts, the repulsion forcesrepulsion
forces
amongamongpolymer polymer
chainschains decrease
decrease due due to shielding
to shielding negativecharges
negative chargeswhich
which cause
cause coiling-up
phenomena [43]. In In some
some cases,
cases, thethe presence
presence of of salts
salts in high concentration might lead to phase
separation (e.g., gel-formation) [44]. The reduction in viscosity due to salinity is more pronounced at
the presence of divalent cations (e.g., Ca Ca2+ , Mg
Mg2+, etc.) compared
compared to that of monovalent cations like
+
Na [43].
Na
The previous study by Skauge et al. [45] demonstrated demonstrated a combination of experiments for
investigating
investigating the thecontributions
contributions of polymer
of polymer molecular weight
molecular and concentration
weight conformational
and concentration regimes
conformational
to its rheological properties. The measurements included shear viscosity
regimes to its rheological properties. The measurements included shear viscosity (rotational (rotational rheometer),
dynamic
rheometer),viscosity
dynamic(small amplitude
viscosity (smalloscillatory shearoscillatory
amplitude SAOS) andshearin-situSAOS)
rheologyand(Bentheimer cores).
in-situ rheology
The study classified
(Bentheimer cores).the investigated
The polymer solutions
study classified into different
the investigated conformational
polymer solutions regimes; dilute,
into different
∗
semi-dilute,
conformational concentrated semi-dilute
regimes; dilute, and gel concentrated
semi-dilute, solutions, based on criticaland
semi-dilute overlap concentration
gel solutions, based(Con ).
SAOS ∗
criticalmeasurements indicated
overlap concentration (C whether
). SAOS the polymer solution
measurements is viscous
indicated whether orthe
elastic dominated
polymer solution at is
a
particular
viscous or concentration.
elastic dominated Theat initial studies showed
a particular a correlation
concentration. between
The initial bulk
studies elasticamodulus
showed G0
correlation
and apparent
between bulk shear
elasticthickening.
modulus The andmore elasticshear
apparent polymer exhibited
thickening. Thehigher
moreresistance factor in
elastic polymer porous
exhibited
media. The studyfactor
higher resistance also revealed
in porous that polymer
media. The conformation regimethat
study also revealed haspolymer
a high influence on itsregime
conformation in-situ
rheological behavior. Shear viscosity data showed that mechanical degradation was
has a high influence on its in-situ rheological behavior. Shear viscosity data showed that mechanical high for high Mw
polymer
degradationdissolved in high
was high for salinity
high Mw brine. Also, mechanical
polymer dissolved in degradation
high salinitywasbrine.
lowerAlso,
for concentrated
mechanical
degradation was lower for concentrated solutions. Recent review with current knowledge on HPAM
polymers flow in porous media concerning theoretical and experimental aspects is given by Skauge
et al. [46].
One of the most critical aspects of HPAM polymer is mechanical degradation. Such an effect
directly influences polymer viscosifying efficiency as well as alters its rheological properties. Both
Energies 2019, 12, 49 4 of 25

solutions. Recent review with current knowledge on HPAM polymers flow in porous media concerning
theoretical and experimental aspects is given by Skauge et al. [46].
One of the most critical aspects of HPAM polymer is mechanical degradation. Such an
effect directly influences polymer viscosifying efficiency as well as alters its rheological properties.
Both HPAM shear thickening behavior and mechanical degradation are well reported [12,47–50].
Mechanical degradation might occur along with the onset of shear thickening [51]. Onset of shear
thickening has received a great attention in the literature as it is an indication of viscoelasticity in
porous medium [50,52–55]. Any alteration of the molecular structure of HPAM through exposing it
to shear rate above or below the onset of shear thickening may change its apparent shear thickening
behavior [56]. Preshearing polymer by exposing HPAM to wellbore mechanical degradation is a
suggested approach to improve its viscoelastic properties which promotes its injectivity [57]. Despite
the efforts that have been made to understand and model polymer mechanical degradation, the
dependence of polymer mechanical degradation on polymer Mw, MWD, concentration, and polymer
transport distance in porous media requires more investigation [12,26,49].
The impact of mechanical degradation on polymer average Mw and molecular weight distribution
(MWD) were examined in different studies. For example, Seright et al. [58] investigated the mechanical
degradation effect on polymer Mw and MWD by using gel permeation liquid chromatography (GPC).
The degraded solutions showed narrower MWD compared to that of undegraded samples. Hence,
degraded polymer solution has a lower polydispersity. This concept was also confirmed by size
exclusion chromatography (SEC) [59] and asymmetric flow field-flow fractionation (AF4) [30,60–62].
Reduction of Mw or change in MWD is the reason for the observed reduction in screen factor [12,63]
that correlates with reduction of resistance factor as well.
Noïk et al. [36] investigated the effect of Mw, concentration and different types of solvents on
the mechanical degradation of HPAM in short glass cylinders packed with sand particles. The high
Mw polymers were subjected to wellbore mechanical degradation through successive reinjection
into porous media. Reinjection process represents the evolution of degradation as a function of
residence time or the length of porous media. Degradation was assessed by observing the change in
intrinsic viscosity of solutions before and after degradation. They found that the degree of degradation
is independent of concentration for dilute solutions and was only dependent on Mw. However,
for concentrated solutions, the degradation increases with concentration and has less dependency on
average Mw.
Several studies attributed HPAM mechanical degradation to the polymer degradation in sandface,
and therefore, understated the effect of polymer residence time or transported distance in porous
media [12,38,49,64,65]. For example, Maerker [12] attributed mechanical degradation to the first
0.5 inch of porous media while Warner [64] attributed it to the first inch of unperforated wellbore
based on studies performed in Berea rock. Müller et al. [51] reported that the mechanical degradation
of HPAM polymers increased with travel distance and progressively degraded until reached an
asymptotic value that depends on the stretch rate which related to Reynold’s number. A recent
study given by Jouenne et al. [66] highlighted the observation of mechanical degradation at entry
face and limited it for the first 6mm of porous media based on studies performed in a ceramic
disk. However, Al-Shakry et al. [67] conducted experimental studies using HPAM polymers that
showed high Mw polymer underwent successive degradation as reinjected into the porous media.
This suggests that the degree of degradation may depend on exposure time and number of exposures to
high strain beside polymer Mw and concentration. The findings were also in line with Åsen et al. [68].
The dependence of mechanical degradation on travelled distance in porous media has a significant
practical consequences specifically when considering the effect on large scale medium such as field
conditions. These observations were also supported by other studies based on analyzing shear viscosity
data alone [69–71].
Despite the current efforts made both experimentally and theoretically to clarify the problem of
mechanical degradation, the current understanding is not complete, and further analyses are required.
Energies 2019, 12, 49 5 of 25

This paper extends our previous work [67] that provides a basis for this study on experimental
investigation of the impact of mechanical degradation on polymer in-situ rheology. This work extends
the analyses to address the influence of polymer physicochemical properties, particularly molecular
weight and concentration on polymer mechanical degradation and its in-situ behavior. Particular
attention was given for the impact of preconditioning the polymer solution prior to injection into the
porous media on polymer in-situ rheology. The study was performed in a realistic porous medium
using high preamble linear Bentheimer core plugs. The results from this paper give an insight into
in-situ rheological behavior of commercial HPAM polymers, which may be beneficial in polymer
screening and designing of polymer flooding EOR operations. The results from this study may also
serve as useful input for simulation models.

2. Material and Methods

2.1. Synthetic Brine

Synthetic brine of 1wt.% NaCl was prepared and filtered through a 0.45 µm cellulose nitrate
filter. The brine composite (NaCl powder) was obtained from Sigma-Aldrich (Munich, Germany).
The prepared filtered brine was employed in the preparation of bulk polymer solutions, core saturation
and permeability measurements.

2.2. Polymer Preparation

Three types of partially hydrolyzed polyacrylamide (HPAM) with 30% degree of hydrolysis
were employed in this study with different concentrations as shown in Table 1. These polymers
are Flopaam 3330 s, 3430 s and 3630 s which are donated as polymer A, B and C, respectively.
These polymers were received in powder form from SNF Floerger. Each polymer was prepared
with low and high concentration within semi-dilute region to provide a low and high degree of
entanglements, respectively. The selected concentration for each polymer was based on overlap
concentration (C∗ ) determined in earlier studies performed by Skauge et al. [45].
The polymer stock solution of 5000 ppm was prepared by gradually dissolving 3.0 g of polymer
powder into the vortex of 1 wt.%NaCl brine under vigorous stirring until the vortex became invisible.
The polymer solution was left under slow mixing at a stirring speed of 150 rpm for at least 24 h before
dilution into required concentration. The polymer was thoroughly sealed during the preparation.
The prepared aqueous polymer solution was incubated at 5 ◦ C inside a fridge and used within two
weeks of preparation to avoid any chance of chemical degradation.

Table 1. Molecular weights and concentrations of polymers.

Polymer Concentration
Polymer Polymer (Flopaam) Type Molecular Weight (106 g/mol = MDa)
(mg/L = ppm)
1000
A 3330 s 8
4000
1000
B 3430 s 12
3000
500
C 3630 s 18
1000

2.3. Shear Viscosity Measurements

Shear viscosity measurements were carried out at room temperature (22 ◦ C) by using a Kinexus
Pro Rheometer (Malvern, UK). The rheometer is equipped with different geometries which make the
measurements more accurate and convenient to conduct based on fluid types and viscosity. Hence,
double-gap geometry was used during the measurements of viscosities lower than 10 cP and cone-plate
Energies 2019, 12, 49 6 of 25

geometry was used for measuring viscosities higher than 10 cP. The viscosity measurements were
fitted by power law model given below:
. n−1
η = Kγ (1)
.
where, η is shear viscosity (cP), γ is shear rate (s−1 ), K is the consistency index (cP.s(n−1) ) and n is the
flow behavior index (dimensionless).
Energies 2018, 11, x FOR PEER REVIEW 6 of 25
2.4. Porous Medium
The experiments were conducted in linear Bentheimer outcrop cores with an average length and
The experiments were conducted in linear Bentheimer outcrop cores with an average length and
diameter of 10 cm and 3.8 cm, respectively. Similar cores of Bentheimer with shorter length of 5 cm
diameter of 10 cm and 3.8 cm, respectively. Similar cores of Bentheimer with shorter length of 5 cm
were also used for prefiltering and preshearing processes. Details of each core are given in results
were also used for prefiltering and preshearing processes. Details of each core are given in results and
and discussion section.
discussion section.
2.5.Experimental
2.5. ExperimentalProcedures
Procedures
Theexperimental
The experimentalsetup
setupdisplayed
displayedininFigure
Figure2 2mainly
mainlyconsists
consistsofofQuizix-QX
Quizix-QXdual
dualpiston
pistonpump,
pump,
transfer cylinder, core holder, pressure transducers, back pressure regulator and effluent collector.
transfer cylinder, core holder, pressure transducers, back pressure regulator and effluent collector.
Notethat,
Note that,backpressure
backpressureregulator
regulatorwas
wasused
usedduring
duringpermeability
permeabilitymeasurements
measurementstotodissolve
dissolveany
anyairairinin
the setup and it was removed during polymer injection to avoid polymer degradation.
the setup and it was removed during polymer injection to avoid polymer degradation.

Figure 2. Schematic diagram of core flooding apparatus used for in-situ rheology experiments.
Figure 2 Schematic diagram of core flooding apparatus used for in-situ rheology experiments.
Core flood experiments were conducted at room temperature (22 ◦ C) and consisted of three stages
Core flood experiments were conducted at room temperature (22 oC) and consisted of three
as detailed in the previous study [67]. The core flood procedure was performed as follows:
stages as detailed in the previous study [67]. The core flood procedure was performed as follows:
2.5.1. Brine Pre-Flush
2.5.1. Brine Pre-Flush
Before injecting the brine, the core plugs were vacuumed and saturated with brine for at least
two daysBefore injecting
to ensure the brine,
achieving the
ionic core plugsbetween
equilibrium were vacuumed and and
the core plug saturated with brine
brine followed byfor at least
porosity
two days to ensure
measurements. Then,achieving ionicwas
the core plug equilibrium
mountedbetween theholder
in the core core plug
andand brine
brine wasfollowed byvarious
injected at porosity
measurements. Then, the core plug was mounted in the core holder and brine was
flow rates to measure absolute permeability (Kabs ) which was calculated according to Darcy’s injected at various
law
flow rates
(Equation to measure absolute permeability (K ) which was calculated according to Darcy’s law
(2)):
(Equation (2)): Q × η × L
Kabs = (2)
∆PQ .
×η .AL
K = (2)
where, Q is injection flow rate, η is fluid viscosity, ∆PΔP. is Apressure drop across the core, L and A are
core length
where, Q isand cross-sectional
injection flow rate,area,
η is respectively. By considering
fluid viscosity, ΔP is pressureDarcy
drop velocity
across the(vDcore,
) which
L andis also
A are
core length and cross-sectional area, respectively. By considering Darcy velocity (v ) which is also
known as superficial flow velocity as Q⁄A, the average or interstitial velocity (v) is given in Equation
(3), where is the porosity of porous media:

= (3)

Darcy velocity v was also applied to calculate reservoir shear rate γ. A conventional formula
was used to estimate reservoir formation shear rate [65]:
Energies 2019, 12, 49 7 of 25

known as superficial flow velocity as Q/A, the average or interstitial velocity (v) is given in Equation
(3), where φ is the porosity of porous media:
vD
v= (3)
φ
.
Darcy velocity vD was also applied to calculate reservoir shear rate γ. A conventional formula
was used to estimate reservoir formation shear rate [65]:

. 4 vD
γ= α p (4)
8 Kabs φ

where, α is formation shape factor which is assumed 2.5 for Bentheimer sandstone [1,38].
Energies 2018, 11, x FOR PEER REVIEW 7 of 25

2.5.2.2.5.2.
Polymer Injection
Polymer Injection
TheTheinvestigated polymers
investigated polymerswerewere
pretreated first before
pretreated injection
first before into the
injection main
into thecores.
mainPretreatment
cores.
processes consisted
Pretreatment of prefiltering,
processes consisted ofreinjecting
prefiltering,and preshearing
reinjecting as illustrated
and preshearing in Figure 3.
as illustrated in Pre-filtering
Figure
and 3.preshearing
Pre-filtering processes
and preshearing
wereprocesses
performed were onperformed on short
short cores (L = cores
5 cm)(Lat= 5low
cm) and
at low and flow
high high rates,
flow rates,Reinjected
respectively. respectively. Reinjected
polymer polymer
has been has beenfirst
prefiltered prefiltered
in shortfirst
coreinthen
short core then
sheared sheared
at high flowatrate in
longhigh
coreflow
(L =rate in long
10 cm). Thecore (L =rate
flow 10 cm).
usedThe
in flow rate used
prefiltering in prefiltering
process was (Qprocess was (Q =v0.5=cc/min,
= 0.5 cc/min, D 0.6 m/day)
v = 0.6 m/day) whereas the flow rates applied in preshearing and reinjecting are given in Table 2.
whereas the flow rates applied in preshearing and reinjecting are given in Table 2. Recall that the
Recall that the purpose of prefiltering was to remove any microgel in the solution and filter out any
purpose of prefiltering was to remove any microgel in the solution and filter out any possible large
possible large Mw species. This step represents available commercial polymers that are utilized in
Mw field
species. This step Prefiltered
applications. representspolymer
availablesolutions
commercial also polymers
serve as athat are utilized
baseline in field applications.
for comparison with
Prefiltered polymer solutions also serve as a baseline for comparison with
presheared and reinjected solutions. Preshearing was carried out to induce partial degradationpresheared and reinjected
in
solutions. Preshearing
which large Mw species wasincarried out to
the solution areinduce partialand
likely filtered degradation
mechanicallyin which
degraded large Mw species
to lower Mw in
the solution are likely
species. While filtered
reinjection wasand mechanically
designed to evaluatedegraded to lower
the evolution of Mw species.
polymer While reinjection
degradation with
was respect
designed to the residence the
to evaluate timeevolution
of polymer ofsolution,
polymercore characteristic
degradation withlength, number
respect to theofresidence
passes and time of
multi entry effects.
polymer solution, core characteristic length, number of passes and multi entry effects.

Figure 3.
Figure Polymerpretreatment
3. Polymer pretreatment processes.
processes.

Table Applied
2. 2.
Table Appliedflow
flowrates for presheared
rates for preshearedand
and reinjected
reinjected polymer
polymer solutions.
solutions.

Polymer Polymer A A B B C C
Concentration (ppm) 1000 4000 1000 3000 500 1000
Concentration (ppm) 1000 4000 1000 3000 500 1000
Q (cc/min) 26 22 15 7 12 6
Q (cc/min) 26 22 15 7 12 6
(m/day) 33.5 28.4 19.4 9.0 15.5 7.7
v D (m/day) 33.5 28.4 19.4 9.0 15.5 7.7
Pretreated polymer solution was injected into the main core at low flow rate (Q = 0.5 cc/min,
v = 0.6 m/day) for at least 2 PV. This was performed to satisfy polymer adsorption level in the core
and achieving steady-state condition (stable differential pressure over time). Then, the injection flow
rate was increased gradually to achieve highest flow rate given in Table 2 and then decreased in a
stepwise manner from highest to lowest flow rate. The polymer injection over wide flow rates was
performed to simulate the velocities that are anticipated near wellbore region and deep in the
Energies 2019, 12, 49 8 of 25

Pretreated polymer solution was injected into the main core at low flow rate (Q = 0.5 cc/min,
vD = 0.6 m/day) for at least 2 PV. This was performed to satisfy polymer adsorption level in the core
and achieving steady-state condition (stable differential pressure over time). Then, the injection flow
rate was increased gradually to achieve highest flow rate given in Table 2 and then decreased in a
stepwise manner from highest to lowest flow rate. The polymer injection over wide flow rates was
performed to simulate the velocities that are anticipated near wellbore region and deep in the reservoir.
Resistance factor (RF) was calculated as follows [72]:

∆Pp
RF = (5)
∆Pw

where, ∆Pp is the pressure drop of the polymer during polymer flow and ∆Pw is the pressure drop of
the brine before polymer flow in the porous medium.
After injecting for at least 1 PV for each step rate and steady-state condition was achieved,
effluent samples of were collected at different flow rates and their shear viscosity was measured by
the rheometer. The following equation was used to express the change in shear viscosity (mechanical
degradation) [66]:
η − ηe
Deg(%) = i × 100 (6)
ηi− ηw
where, ηi is injected solution viscosity, ηe is effluent viscosity and ηw is brine viscosity which was
measured to be 1.04 cP. The viscosity data used in this equation were measured at the shear rate of
10 s−1 .

2.5.3. Brine Post-Flush

After terminating the polymer injection, tapering was performed by injecting 5 PV of diluted
polymer effluent with 50 and 25% of initial effluent concentration. During tapering the injection of
the diluted polymer was performed at low flow rate (Q = 1.0 cc/min, vD = 1.3 m/day) for 1 PV
then gradually increased to higher flow rates. After tapering with polymer, brine was injected at
low flow rate (Q = 0.5 cc/min, vD = 0.6 m/day) for 1 PV then the injection rate was increased in a
stepwise manner. The final permeability to brine was measured after flushing 5 PV of brine at high
rates proceeded by two steps of tapering. Tapering was performed in an effort to approach ‘true’
residual resistance factor (RRF) which was calculated using Equation (7) [72]:

Kwi
RRF = (7)
Kwf

where, Kwi and Kwf are the absolute permeability’s to brine before and after polymer flow in porous
media, respectively. These values were calculated by using Equation (2).

3. Results and Discussion

3.1. Shear Viscosity

The bulk shear viscosity of polymer solutions was measured in the rheometer at a wide range
of shear rates as shown in Figure 4. At the mid-range of shear rates, all the solutions exhibited a
predominant shear thinning behavior. The measurements were showed a good fit to the power law
model (Equation (1)) using the fitting parameters given in Table 3. Concentrated solutions showed a
higher slope of shear thinning behavior compared to the solutions with lower concentration as seen
in Figure 4. Accordingly, the flow behavior index n decreases as polymer concentration increases
(see Table 3) and vice versa for the consistency index K. This is due to the high degree of entanglements
present in concentrated solutions. Hence polymer molecules are more sensitive to imposed shear rate
that reduces the degree of entanglements resulting in lower viscosity with increasing flow rates [73].
Energies 2019, 12, 49 9 of 25

Shear viscosity increases with increasing polymer molecular weight or concentration. For a given
polymer concentration of 1000 ppm, the shear viscosity of polymer A, B and C were 8.4, 13.6 and
.
19.0 cP, respectively, measured at γ = 10 s−1 . We are using a shear rate of 10 s−1 in this study as a
reference of reservoir relevant shear rate. The increase of viscosity with Mw is ascribed to increase in
hydrodynamic volume and charge density per molecule. On the other hand, the increase of viscosity
with respect to concentration is ascribed to the increase of the number of molecules that increases the
interaction and 11,
Energies 2018, repulsion forces
x FOR PEER among negatively charged polymer molecules [6].
REVIEW 9 of 25

4. Shear viscosity of of
prefiltered ◦ C. Solid lines
Figure
Figure 4 Shear viscosity prefilteredbulk
bulksolutions A,BBand
solutions A, andCCinin1 wt.
1 wt.
%% NaCl
NaCl ato22
at 22 C. Solid lines
represent the power
represent lawlaw
the power model.
model.

Table 3. Power
Table law
3. Power fitting
law fittingparameters
parameters K, n and
K, n andcoefficient
coefficientofof determination. R2 .
determination R

Polymer
Polymer A A B B C C
Concentration (ppm) 1000 4000 1000 3000 500 1000
Concentration ) (ppm) 1000 4000 1000 3000 500 1000
K (cP.s( (n−)1) 12.30 207.98 25.17 268.52 11.17 38.99
K (cP.s ) 12.30 207.98 25.17 268.52 11.17 38.99
n 0.84 0.60 0.73 0.52 0.80 0.69
R 2
n 0.84
0.93
0.600.95 0.730.97 0.52 1.00 0.80 0.99 0.69 0.98
R 0.93 0.95 0.97 1.00 0.99 0.98
3.2. In-Situ Polymer Rheology
3.2. In-Situ Polymer Rheology
3.2.1. Apparent Viscosity in Porous Medium vs Bulk Viscosity in Rheometer
3.2.1. Apparent Viscosity in Porous Medium vs Bulk Viscosity in Rheometer
In this study, polymer apparent viscosity in the porous medium is represented by resistance
factor
In this(RF) as apolymer
study, function apparent
of interstitial velocity.
viscosity inHowever, translating
the porous mediumpolymer flow velocity
is represented in porousfactor
by resistance
medium to shear rate is required to correlate flow velocity in porous medium
(RF) as a function of interstitial velocity. However, translating polymer flow velocity in porous with the shear ratemedium
in
rheometer. Determining the shear rate in porous medium is challenging due to many factors such as
to shear rate is required to correlate flow velocity in porous medium with the shear rate in rheometer.
wide pore size distributions, tortuosity and complexity of porous media. A conventional formula
Determining the shear rate in porous medium is challenging due to many factors such as wide pore size
given in Equation (4) was used to estimate reservoir formation shear rate. Figure 5 shows the viscosity
distributions,
profiles oftortuosity
polymer Band (3000 complexity
ppm) in porous of porous
mediummedia. A conventional
versus formula
bulk shear viscosity given
in the in Equation
rheometer.
(4) was used to estimate
Resistance factor andreservoir
apparentformation shear rate.
viscosity profiles Figure in
of polymer 5 shows
porousthe viscosity
media profiles of The
were consistent. polymer
B (3000 ppm)exhibited
polymer in porous medium versus
a predominantly shearbulk shearbehavior
thinning viscosityinin the rheometer.
rheometer Resistance
while it exhibited factor and
different
apparent
flow viscosity
behaviors profiles
in porousofmedia.
polymer rates γmedia
in porous
At shear < 30 swere
, theconsistent. The polymer
polymer exhibited exhibited a
shear thinning
behavior in porous
predominantly media while
shear thinning shear thickening
behavior in rheometer behavior
whilewasitobserved
exhibited at shear γ > 52
ratesflow
different s . A in
behaviors
near-Newtonian behavior .
porous media. At shear rateswasγ < observed
30 s−1 , the during the transition
polymer exhibitedbetween shear thinning
shear thinning behavior to shear
in porous
thickening behaviors. Both in-situ behaviors (near-Newtonian and .
shear thickening)
− 1 in porous
media while shear thickening behavior was observed at shear rates γ > 52 s . A near-Newtonian
medium were not predicted by shear rheology. This is expected due to the different nature of flow
behavior was observed during the transition between shear thinning to shear thickening behaviors.
exists in porous medium which is not purely shear flow as in rheometer [37].
Both in-situ behaviors (near-Newtonian and shear thickening) in porous medium were not predicted
Figure 5 shows bulk shear viscosity decreased while the apparent viscosity increased. For
by shear rheology.
example, at γ ≈This
400 iss expected
, bulk sheardue to the different
viscosity nature
was 16.7 cP while of flow exists
apparent in porous
viscosity was ~300medium
cP which which
is notispurely shear flow as in rheometer [37].
more than 10 times higher than bulk shear viscosity. This indicates the contribution of extensional
viscosity to apparent viscosity at high flow rates. Polymer apparent viscosity is a combination of
shear and extensional viscosity of viscoelastic polymers [1].
Energies 2019, 12, 49 10 of 25

Figure 5 shows bulk shear viscosity decreased while the apparent viscosity increased. For example,
.
at γ ≈ 400 s−1 , bulk shear viscosity was 16.7 cP while apparent viscosity was ~300 cP which is more
than 10 times higher than bulk shear viscosity. This indicates the contribution of extensional viscosity
to apparent viscosity at high flow rates. Polymer apparent viscosity is a combination of shear and
extensional viscosity
Energies 2018, ofPEER
11, x FOR viscoelastic
REVIEW polymers [1]. 10 of 25

FigureFigure 5. Viscosity
5. Viscosity profiles
profiles of of prefilteredPolymer
prefiltered Polymer BB(3000
(3000ppm)
ppm)as as
measured in the
measured inporous medium
the porous medium
and in
and in bulk. bulk.

3.2.2. 3.2.2.
FlowFlow of Semi-Dilute
of Semi-Dilute PolymerSolutions
Polymer Solutions

Figure Figure 6 depicts

6 depicts theresistance
the resistance factor
factorof of polymer
polymer A, B A,andBCand versus
C interstitial velocity. The
versus interstitial velocity.
concentration of polymer A and B was 1000 ppm while for polymer C was 500 ppm. Shear viscosity
The concentration of polymer A and B was 1000 ppm while for polymer C was 500 ppm. Shear
data of prefiltered solutions A, B and C were 8.4, 13.5 and 7.1 cP, respectively, as tabulated in Table
viscosity data of prefiltered solutions A, B and C were 8.4, 13.5 and 7.1 cP, respectively, as tabulated
4. At low velocities all the polymers exhibited near-Newtonian behavior followed by shear thickening
in Table 4. At
at high low velocities
velocities. all the polymers
This represents the generalexhibited
behavior ofnear-Newtonian
polymer flow in porous behavior
mediumfollowed
for semi-by shear
thickening at high velocities. This represents the general behavior of polymer
dilute solutions. Similar observations have been reported elsewhere [11,12,49,50,74]. The RF curves flow in porous medium
for semi-dilute
are strongly solutions.
dependent Similar
on polymerobservations
molecular have beenFor
weight. reported
example, elsewhere [11,12,49,50,74].
RF at reservoir velocities ofThe RF
curvespolymer A was dependent
are strongly 2 times lower onthan that of molecular
polymer polymer B whichweight. was ~ 18.4.
For Similarly,
example, shear
RF at thickening
reservoir velocities
behavior was more dramatic for polymer C with high Mw. This could
of polymer A was 2 times lower than that of polymer B which was ~ 18.4. Similarly, shear thickening be observed from the earlier
onset of shear thickening for polymer C (v = 2.5 m/day) to that of polymers B and A (v = 4.1 and
behavior was more dramatic for polymer C with high Mw. This could be observed from the earlier
7.0 m/day, respectively). Moreover, the stronger viscoelastic properties of high Mw polymer C can
onset of shear thickening for polymer C (vc = 2.5 m/day) to that of polymers B and A (vc = 4.1 and
be observed from the slope of apparent shear thickening 7.7 (m/day) compared to 3.5 and 0.5
7.0 m/day,
(m/day) respectively).
for polymerMoreover, the stronger
B and A, respectively. Thisviscoelastic
yields higherproperties
RF values for of high
polymerMw C polymer
(RF ~196) C can
−1
be observed from the slope of apparent shear
at high flow rate compared to that of lower Mw polymers. thickening 7.7 ( m/day ) compared to 3.5 and 0.5
(m/day)−It1 isfor polymer B and A, respectively. This yields higher RF values
worth noting that effluents shear viscosity of prefiltered solutions for polymers A and for polymer C (RF
B did~196) at
not show
high flow rate significant
comparedmechanical
to that ofdegradation
lower Mw at the investigated flow velocities. However, prefiltered
polymers.
Itpolymer
is worth C showed
noting that degradation
effluents at shear
high velocities
viscosity(Deg = 21.7%). This
of prefiltered could befor
solutions thepolymers
reason forA lower
and B did
RF values for reinjected polymer C in Figure 6c.
not show significant mechanical degradation at the investigated flow velocities. However, prefiltered
Reinjection process was carried out to simulate the polymer flow deep in the reservoir (radially
polymer C showed degradation at high velocities (Deg = 21.7%). This could be the reason for lower RF
distant from the wellbore). This process also demonstrates the effect of exposure time at high shear
valuesonfor reinjected
polymer polymer
degradation. In C inprocess,
this Figure the6c. polymer solution passed two cores at different flow rates
Reinjection
before measuring process wasrheology
in-situ carriedinout theto simulate
main thefirst
core. The polymer
core (5 flow deepwas
cm length) in the
used reservoir
for the pre- (radially
distant from the
filtering processwellbore). Thisrate
at low flow process
(Q = 0.5also demonstrates
cc/min), the effect
while the second core of
(10exposure
cm length)timewas at high
used as shear
on polymer
shearingdegradation.
media. Hence,Inthis this process,
process the from
differs polymer solution passed
the presheared polymertwo coresinatwhich
process different
the flow
polymermeasuring
rates before solution wasin-situ
shearedrheology
in a short incoretheand at high
main flowThe
core. velocity
firstbefore
core (5thecm
measurement
length) was of in-
used for
situ rheology in the main core (see Figure 3 for details). Therefore, the
the pre-filtering process at low flow rate (Q = 0.5 cc/min), while the second core (10 cm length) results will be compared with was
preshearing process. Pretreatment methods (reinjection and preshearing) caused a reduction of RF
used as shearing media. Hence, this process differs from the presheared polymer process in which
values at high velocities while RF values were similar to prefiltered solution at low velocities. This
the polymer solution was sheared in a short core and at high flow velocity before the measurement
could be clearly seen from the shift of the onset to higher velocities and reduction on the degree of
of in-situ rheology
shear thickening. in the main core
In Figure 6a, RF(see Figure
profile of 3reinjected
for details). Therefore,
polymer the results
A indicates more will be compared
degradation
with preshearing
occurred compared process. Pretreatment
to presheared methods
solution. This is (reinjection
analogous to the andobservation
preshearing) shown caused a reduction
in Figure 6c
for polymer C at low concentration. This confirms the occurrence of successive degradation as the
polymer was reinjected in porous media which is inline with some other studies [68,75]. However,
Energies 2019, 12, 49 11 of 25

of RF values at high velocities while RF values were similar to prefiltered solution at low velocities.
This could be clearly seen from the shift of the onset to higher velocities and reduction on the degree of
shear thickening. In Figure 6a, RF profile of reinjected polymer A indicates more degradation occurred
compared to presheared solution. This is analogous to the observation shown in Figure 6c for polymer
C at low concentration. This confirms the occurrence of successive degradation as the polymer was
reinjected Energies
in porous
2018, 11, media which
x FOR PEER REVIEW is inline with some other studies [68,75]. However, 11 of 25this was not
observed for polymer B. The successive polymer degradation observed in this study in contrast to the
this was not observed for polymer B. The successive polymer degradation observed in this study in
current understanding of mechanical degradation which is mainly confined to sand face degradation
contrast to the current understanding of mechanical degradation which is mainly confined to sand
and is believed to be independent
face degradation oftotravelled
and is believed distance
be independent in porous
of travelled media
distance [38,49,66].
in porous media [38,49,66].

(a)

(b)

(c)

FigureFigure
6. 6.Resistance
Resistance factor versus interstitial velocity for semi-dilute polymers A, B and C. Open markers
factor versus interstitial velocity for semi-dilute polymers A, B and C.
indicate effluent shear viscosity for the given velocity measured at γ = 10 . (a) Polymer A (Mw ≈ 8 MDa,.
Open markers indicate effluent shear viscosity for the given velocity measured at γ = 10 s−1 .
(a) Polymer A (Mw ≈ 8 MDa, Concentration = 1000 ppm); (b) Polymer B (Mw ≈ 12 MDa, Concentration
= 1000 ppm); (c) Polymer C (Mw ≈ 18 MDa, Concentration = 500 ppm).
Energies 2019, 12, 49 12 of 25

The difference between shear viscosity of effluents and resistance factor values at low velocities
was different depending on polymer type. This indicates that the difference in polymer retention
correlates with the increase of polymer molecular weight. That is, the difference between RF values
and effluent viscosity at similar velocities increases with the increase of polymer molecular weight.
For instance, Newtonian RF values were ~9, 18, 12 with bulk shear viscosity of 8.4, 13.5 and 7.1 cP for
prefiltered polymers A, B and C, respectively.

Table 4. Cores and viscoelastic properties of semi-dilute polymers at concentration of 1000 ppm for
polymers A and B, and 500 ppm for polymer C.

L D φ Kwi Kwf RRF ηi ηe vc m

Experiment
(cm) (cm) (-) (Darcy) (Darcy) (-) (cP) (cP) (m/day) (m/day)−1
Polymer A Pre-Filtered 9.28 3.79 0.23 1.81 1.12 1.61 8.44 8.19 6.98 0.54
Polymer A Re-Injected 9.74 3.79 0.23 2.26 1.16 1.95 8.19 8.28 16.92 0.53
Polymer A Pre-Sheared 10.22 3.77 0.24 2.40 1.48 1.62 8.52 8.42 15.79 0.66
Polymer B Pre-Filtered 9.82 3.79 0.23 2.16 0.96 2.24 13.57 13.31 4.06 3.50
Polymer B Re-Injected 9.57 3.79 0.23 2.08 1.24 1.68 13.31 12.75 7.69 2.28
Polymer B Pre-Sheared 10.27 3.77 0.23 2.80 1.54 1.82 13.54 12.75 11.99 1.46
Polymer C Pre-Filtered 9.82 3.77 0.24 2.57 1.40 1.84 7.11 5.79 2.51 7.68
Polymer C Re-Injected 9.78 3.77 0.24 2.39 1.28 1.86 5.79 - 6.71 3.00
Polymer C Pre-Sheared 9.72 3.77 0.24 2.25 0.82 2.75 7.13 7.21 4.00 4.32

3.2.3. Flow of Concentrated Polymer Solutions

The behavior of concentrated polymer solutions (C >> C∗ ) in porous media seems to be dominated
by shear viscosity that overrides their elastic properties. In such solutions, the interaction between
polymer molecules is dominant and polymer chains are entangled [11]. Figure 7 shows apparent
shear thinning, near-Newtonian and shear thickening behaviors which become very important flow
aspects for high concentrated polymer solutions with high shear viscosity. For instance, Figure 7a
depicts the flow of polymer A at concentration of 4000 ppm in porous media, in particular parlance,
it exhibits pseudo-gel behavior. As this figure shows for prefiltered polymer A, at high velocities
(v > 31.0 m/day) weak shear thickening behavior is observed with slight increase in RF values
compared to near-Newtonian plateau at flow velocities 5.7 < v < 31.0 m/day. RF values corresponding
to shear thickening behavior are lower than shear viscosity. This suggests that the contribution of
extensional viscosity is lower than that of shear viscosity which dominates the polymer flow behavior.
Below v < 5.7 m/day, the RF values increase with decreasing flow velocity indicating strong shear
thinning behavior. Similar trend was observed for relatively higher Mw polymer B except that the shear
thickening becomes stronger (see Figure 7b). This confirms that the concentration or in other words,
solution conformational regime, has an obvious influence on polymer in-situ rheology. However,
concentrated high Mw polymer C (Figure 7c) exhibits near-Newtonian behavior at lower shear rates
that are analogous to semi-dilute polymers discussed earlier without the presence of shear thinning
behavior. This could be ascribed to lower shear viscosity of polymer C at 1000 ppm compared to the
other two polymers A and B. Higher molecular weight polymers possess higher RF at high velocity
than the low Mw polymers with higher concentration. This also indicates the contribution of higher
elastic properties such as elastic viscosity compared to that of lower Mw solutions.
Energies 12, 4911, x FOR PEER REVIEW
2019, 2018,
Energies 13 of 2513 of 25

(a)

(b)

(c)
Figure 77.
Figure Resistance factorfactor
Resistance versusversus
interstitial velocity for
interstitial concentrated
velocity polymers A B and
for concentrated C at concentration
polymers A B and C at
of 4000 3000 and 1000 ppm, respectively. Open markers indicate effluent shear viscosity for the given
concentration of 4000 3000 and 1000 ppm, respectively. Open markers indicate effluent shear viscosity
velocity measured at γ = 10 𝑠 . (a) Polymer
. A (Mw ≈ 8 MDa, Concentration = 4000 ppm); (b) Polymer B
for the given velocity measured at γ = 10 s−1 . (a) Polymer A (Mw ≈ 8 MDa, Concentration = 4000
(Mw ≈ 12 MDa, Concentration = 3000 ppm); (c) Polymer C (Mw ≈ 18 MDa, Concentration = 1000 ppm). Commented [M2]: 图
ppm); (b) Polymer B (Mw ≈ 12 MDa, Concentration = 3000 ppm); (c) Polymer C (Mw ≈ 18 MDa,
Concentration = 1000
The existence ppm).thinning in porous media is conditional and argued by Seright et al. [76]
of shear
at which they attribute shear thinning to the presence of micro-gels in polymer solution. However, Commented [BA3R2
The existence of shear thinning in porous media is conditional and argued by Seright et al. [76]
at which they attribute shear thinning to the presence of micro-gels in polymer solution. However,
the results in Figure 7 show a contradictory observation and confirm the existence of shear thinning
Energies 2019, 12, 49 14 of 25

phenomena for concentrated solution in porous media even if the polymer has been pre-filtered or
presheared (microgel-free).
Exposing the polymer to wellbore mechanical degradation alters its viscoelastic behavior through
the shift of Newtonian plateau and onset of shear thickening to higher velocities as is seen in Figure 7
for both reinjected and presheared solutions A and B. However, insignificant alteration occurs on
shear thinning part. Effluent viscosity of reinjected solution B suffers more degradation compared
to presheared sample which could be due to attachment of backpressure device that might induce
additional degradation to polymer solution [67]. RF curves of degraded solutions C (reinjected and
presheared) are coincident which indicates that the solution tolerates wellbore mechanical degradation
compared to semi-dilute solution with same polymer C discussed above (see Figure 6c). However,
the RF curves of degraded solution C were lower than prefiltered solution which could be due to
filtration effect and also lower RRF (see Table 5).

Table 5. Cores and viscoelastic properties of concentrated polymers A, B and C at concentration of

4000, 3000 and 1000 ppm, respectively.

L D φ Kwi Kwf RRF ηi ηe vc m

Experiment
(cm) (cm) (-) (Darcy) (Darcy) (-) (cP) (cP) (m/day) (m/day)−1
Polymer A Pre-Filtered 9.69 3.77 0.23 2.75 1.48 1.86 83.02 79.31 31.00 0.37
Polymer A Re-Injected 10.05 3.74 0.23 2.53 1.58 1.60 79.31 76.74 43.00 0.43
Polymer A Pre-Sheared 9.95 3.77 0.23 2.50 1.84 1.36 77.91 - 42.00 0.45
Polymer B Pre-Filtered 9.85 3.79 0.22 2.40 0.73 3.31 88.76 85.90 4.37 8.45
Polymer B Re-Injected 9.52 3.78 0.22 2.64 1.04 2.53 85.90 66.12 11.21 2.96
Polymer B Pre-Sheared 9.93 3.78 0.22 2.35 0.85 2.77 83.79 80.79 9.08 3.59
Polymer C Pre-Filtered 10.04 3.78 0.22 2.12 0.23 9.27 18.95 17.98 2.31 16.07
Polymer C Re-Injected 9.81 3.78 0.22 2.01 0.33 6.09 17.98 17.46 3.78 9.71
Polymer C Pre-Sheared 9.68 3.78 0.23 2.37 0.80 2.96 17.86 17.14 3.40 8.47

3.2.4. Onset and Slope of Shear Thickening Behavior

Figure 8 presents the resistance factor change for prefiltered polymers A, B and C at different
concentrations. As this figure shows, RF is influenced by both polymer molecular weight and
concentration. That is, RF gains strength with increasing Mw and concentration. This is inline with
the increase in shear viscosity shown in Figure 4 where shear viscosity increases with increase in Mw
and concentration. However, the impact of Mw and concentration on RF values in the porous media
is a function of velocity. RF is dominated by molecular weight at high velocities to a greater extent
than concentration and vice versa at low velocities below the onset of shear thickening. For instance,
RF curves of polymer A converge to similar values at high velocities regardless of the significant
difference in concentration while the concentration differentiates the RF at low velocities. This indicates
the contribution of both shear and elastic viscosity in polymer flow through porous media, although
shear viscosity reaches its minimum at high velocities [74]. The degree and magnitude of shear
thickening increase with the increase in molecular weight and concentration. This highlights the
influence of shear and elastic viscosities on the slope of apparent shear thickening [37].
The onset of shear thickening and the flow behavior of polymer are more important than the
extensional magnitude itself in determining the suitability of polymer for EOR applications [77]. Hence,
onset of shear thickening has received extensive attention in the literature [50,52,53,78]. Figure 8 shows
polymer molecular weight has an obvious influence on the onset of shear thickening. A solution
with higher molecular weight experiences earlier onset of shear thickening. With increasing polymer
Mw, the apparent shear thickening increases, conversely, the onset of shear thickening shifts to lower
velocities [79].
Moreover, Figure 8 shows that onset of shear thickening is independent of polymer concentration.
This observation excludes 4000 ppm polymer A which exhibits a gel-like behavior and yields shift
of the onset to higher velocities. This confirms that the conformational state of polymer solution has
more influence on the onset of shear thickening compared to the concentration value itself. This could
be one of the reasons that cause a controversial observations in the literature regarding the correlation
 solution with higher molecular weight experiences earlier onset of shear thickening. With increasing
polymer Mw, the apparent shear thickening increases, conversely, the onset of shear thickening shifts
to lower velocities [79].
Moreover, Figure 8 shows that onset of shear thickening is independent of polymer
concentration. This observation excludes 4000 ppm polymer A which exhibits a gel-like behavior and
Energies
yields2019, 12, of
shift 49 the onset to higher velocities. This confirms that the conformational state of polymer 15 of 25
solution has more influence on the onset of shear thickening compared to the concentration value
itself. This could be one of the reasons that cause a controversial observations in the literature
between the onset and polymer concentration. For example, Chauveteau and Moan [52] reported
regarding the correlation between the onset and polymer concentration. For example, Chauveteau
the onset of shear thickening decreases with increasing polymer concentration for investigated wide
and Moan [52] reported the onset of shear thickening decreases with increasing polymer
concentration range (21–1360 ppm). However, a close look on the reported data, we could see
concentration for investigated wide concentration range (21–1360 ppm). However, a close look on the
thereported
onset was data,almost
we couldsimilar
see thefor a specific
onset concentration
was almost similar for arange (e.g.,
specific 170–680 ppm).
concentration This170–
range (e.g., again
indicates
680 ppm). This again indicates the conformational state influences the onset of shear thickening. For a
the conformational state influences the onset of shear thickening. For instance, within
semi-dilute regime,a the
instance, within onset ofregime,
semi-dilute shear thickening decreases
the onset of with molecular
shear thickening weight
decreases with increases
molecularregardless
weight
of increases
concentration [79,80]. The apparent viscosity from the resistance factor gradually
regardless of concentration [79,80]. The apparent viscosity from the resistance increases
factor as
polymer
graduallyconcentration
increases asincreases [81].
polymer concentration increases [81].

Figure Resistancefactor
Figure8.8 Resistance factor versus
versus interstitial
interstitial velocity
velocity for prefiltered
for prefiltered polymers
polymers A, B and A,
C atBdifferent
and C at
concentrations.
different concentrations.

3.3.3.3.
Polymer Mechanical
Polymer MechanicalDegradation
Degradation
The
Thepresented
presentedresults
resultsshowed
showedthe theimpact
impact of wellbore
wellboremechanical
mechanicaldegradation
degradation onon both
both bulk
bulk shear
shear
viscosity and
viscosity andin-situ
in-siturheology.
rheology.Despite
Despite the
the insignificant impactofofmechanical
insignificant impact mechanicaldegradation
degradation onon shear
shear
viscosity ofof
viscosity effluents,
effluents,a aconsiderable
considerablealteration
alteration of in-situ
in-situ rheology
rheologybehavior
behavioroccurred.
occurred. The
The significant
significant
alterationwas
alteration wasfound
found with
with reduction
reduction of ofapparent
apparentshear
shearthickening
thickening behavior
behaviorby shifting its onset
by shifting to
its onset
to higher
higher velocity
velocityand
andreduction
reductionofofthe theslope
slopewhile
whilemaintaining
maintainingin-situ
in-situviscosity.
viscosity.TheTheamount
amount of of
alteration
alteration wasinfluenced
was influencedby by polymer
polymer conformational
conformationalregime.
regime. ForFor
instance, the the
instance, change of the
change ofonset of
the onset
shear thickening by comparing presheared solution A with a prefiltered
of shear thickening by comparing presheared solution A with a prefiltered sample was 126.2% sample was 126.2% at at
concentration of 1000 ppm, while this percentage drops to 35.5% when polymer
concentration of 1000 ppm, while this percentage drops to 35.5% when polymer concentration increases concentration
to increases
4000 ppm.to 4000
Thisppm. This valid
is also is also for
valid for polymers
polymers B andB and
C. C. Thiselucidates
This elucidates that
thatincreasing
increasing polymer
polymer
concentration is beneficial for polymer shear stability [36,82]. However, the impact of mechanical
concentration is beneficial for polymer shear stability [36,82]. However, the impact of mechanical
degradation on the slope of shear thickening was independent of polymer conformation regime
degradation on the slope of shear thickening was independent of polymer conformation regime
(concentration). For example, the change of the slope of shear thickening of presheared solution B
(concentration). For example, the change of the slope of shear thickening of presheared solution B
compared to prefiltered sample was 58.6% at concentration of 1000 ppm while it was 57.5% when
compared to prefiltered sample was 58.6% at concentration of 1000 ppm while it was 57.5% when
polymer concentration increased to 3000 ppm. Similar observations were found for the other two
polymers. This indicates that the impact of wellbore mechanical degradation on shifting onset of shear
thickening to higher velocities was lower for concentrated solutions compared to that of semi-dilute
polymer solutions. The change in the slope of shear thickening due to mechanical degradation seems
independent of concentration.
polymer concentration increased to 3000 ppm. Similar observations were found for the other two
polymers. This indicates that the impact of wellbore mechanical degradation on shifting onset of
shear thickening to higher velocities was lower for concentrated solutions compared to that of semi-
dilute polymer solutions. The change in the slope of shear thickening due to mechanical degradation
seems
Energiesindependent
2019, 12, 49 of concentration. 16 of 25

3.3.1. Influence of Mechanical Degradation on In-Situ Rheology

3.3.1. Influence of Mechanical Degradation on In-Situ Rheology
Figure 9 compares the impact of mechanical degradation on the reduction of RF values of high
Figure 9 compares
Mw polymers B and C tothe RFimpact of mechanical
of prefiltered polymer degradation
A which has on relatively
the reductionlowerof Mw.
RF values
Recalloffrom
high
Mw polymers B and C to RF of prefiltered polymer A which has relatively lower
the discussion above, polymer Mw is a dominating factor on the polymer flow behavior after onset Mw. Recall from the
ofdiscussion above, polymer
shear thickening Mw is apolymers.
for semi-dilute dominating factor onofthe
Reduction polymer
slope flowof
and shift behavior
onset ofafter
shearonset of shear
thickening
tothickening for semi-dilute
higher velocities polymers.of
is an indication Reduction of slope
a reduction and shiftMWD
of polymer of onset of For
[50]. shear thickening
example, thetodegree
higher
velocities is an indication of a reduction of polymer MWD [50]. For example,
was reduced and onset of shear thickening of high Mw Polymer C (Mw ≈ 18 MDa) shifted to higher the degree was reduced
and onsetdue
velocities of shear thickeningTherefore,
to preshearing. of high Mw RFPolymer C (Mwto≈that
curve similar 18 MDa) shifted
of lower Mw to higher velocities
prefiltered Polymerdue B
to preshearing. Therefore, RF curve similar to that of lower Mw prefiltered
(Mw ≈ 12 MDa) was achieved. A similar observation was found for presheared polymer B where Polymer B (Mw ≈ 12 MDa)
was achieved.
preshearing A similar
resulted observation
in shifting was found
RF values closerfor presheared
to RF polymer
of prefiltered B where
polymer preshearing
A (Mw ≈ 8 MDa). resulted
This
in shifting
was RF values
also observed for closer to RF ofsolutions
concentrated prefilteredaspolymer
shown on A the ≈ 8 Figure
(Mwright MDa). 9. This was also observed for
concentrated solutions as shown on the right Figure 9.

(a) (b)
Figure
Figure99.Influence
Influenceofofpreshearing
preshearingonondegrading
degradingthe
theresistance
resistancefactor
factorofofhigh
highMw
Mwpolymers
polymerstotothat
thatofof
lower
lower Mw prefilteredsolutions.
Mw prefiltered solutions.
(a) (a) Semi-dilute
Semi-dilute polymer
polymer solutions;
solutions; (b) Concentrated
(b) Concentrated polymer polymer
solutions.
solutions.
3.3.2. Mechanical Degradation at Elevated Velocities
3.3.2. Mechanical Degradation
Figure 10 displays at Elevated
the effect Velocities
of mechanical degradation on shear viscosity of effluent polymer
solutions
Figureat10a broad range
displays theofeffect
shearofrates. These experiments
mechanical were
degradation on designed to compare
shear viscosity the degradation
of effluent polymer
effect in different polymers which have been exposed to comparable shear rate.
solutions at a broad range of shear rates. These experiments were designed to compare the It is clear that
polymer C with
degradation effecthigh Mw experienced
in different polymersmorewhichshear
havedegradation at to
been exposed similar injection
comparable raterate.
shear applied
It is for all
clear
solutions. For instance, degradation at Q = 90 cc/min was 4.0%, 12.0%, 20.0% for polymers
that polymer C with high Mw experienced more shear degradation at similar injection rate applied A, B and
C, all
for respectively.
solutions. For instance, degradation at Q = 90 cc/min was 4.0%, 12.0%, 20.0% for polymers A,
B and C, respectively.
Energies 2019, 12, 49 17 of 25
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FOR PEER
PEER REVIEW
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Figure 10.
Figure 10 Shear
10 Shear degradation
Sheardegradation at
degradation at elevated
at elevated velocities
elevated velocities for
velocities for polymer
for polymer A,
polymer A, BB and
A, B and C.
and C.
C.

Figure 11
Figure 11 shows
shows the the in-situ
in-situ flow
in-situ flow of of polymer
polymer B
polymer B that
B that has
that has been
has been presheared
been presheared at
presheared at different
at different flow
different flow rates.
flow rates.
rates.
Fresh (undegraded) solution
Fresh (undegraded)
(undegraded) solutionis
solution isisthe
thesame
the samesolution
same solutiondescribed
solution describedin
described ininFigure
Figure
Figure 1010
10 that
that
that has
hashas a shear
aa shear
shear viscosity
viscosity
viscosity of
of
of 13.3
13.3 cP cP
and and
was was injected
injected into into
shortshort Bentheimer
Bentheimer corecore
at at various
various injection
injection
13.3 cP and was injected into short Bentheimer core at various injection rates. It can be seen that the rates.
rates. It canIt can
be be
seen seen
that that
the
the profile
RF
RF RF profile
profile of of fresh
of fresh
fresh solution
solution
solution is is identical
is identical
identical RFtoprofile
to RF
to RF profile
profile of prefiltered
of prefiltered
of prefiltered solution
solution
solution at similar
at similar
at similar velocities.
velocities.
velocities. This
This
This indicates that prefiltering at low flow rates (Q ≤ 0.5 cc/min, ≤ 0.6 m/day)
v
indicates that prefiltering at low flow rates (Q ≤ 0.5 cc/min , ≤ 0.6 m/day) will not alter RF values.
indicates that prefiltering at low flow rates (Q ≤ 0.5 cc/min , D ≤ 0.6 m/day)
will not will
alternotRF alter RF
values.
values.
However, However,
increasingincreasing
preshearingpreshearing
rate
However, increasing preshearing rate to (Q = 15 cc/min, to rate
(Q to
= (Q
15 = 15
cc/min, cc/min, = 19.4 m/day)
v = 19.4
= 19.4 m/day)
D m/day)
will will significantly
significantly
will significantly alter alter
alter viscoelastic
viscoelastic
viscoelastic properties
properties
properties suchsuch
such as the
as as the
the onset
onset onset
andand
and degree
degree
degree ofofshear
of shearthickening,
shear thickening,while
thickening, whilenot
while not significantly
not significantly
affecting in-situ
in-situ viscosity
viscosity and
and bulk
bulk shear
shear viscosity.
viscosity. However,
However,
affecting in-situ viscosity and bulk shear viscosity. However, preshearing the polymer at preshearing
preshearing the the
polymer polymerat very
veryat high
very
high
high injection
injection rate
injection rate (Qrate (Q
(Q == 110 = 110
110 cc/min, cc/min,
cc/min, = D141.2 m/day
=v 141.2 m/day )) causes
= 141.2 m/day) causes
causes aa shear a shear degradation
shear degradation
degradation of of
of 16% 16%
16% and andand aa
a considerable
considerable
considerable reduction(>
reduction
reduction (>(>50%)
50%)on
50%) on onin-situ
in-situviscosity
in-situ viscosityby
viscosity bycomparing
by comparingits
comparing its Newtonian
its Newtonian plateau
Newtonian plateau that
plateau that was
that was
observed in
observed in porous
porous media
media with prefiltered solution.
with prefiltered The reduction
solution. The reduction of of polymer
polymer viscoelastic
viscoelastic properties
properties
such as
such as the
the onset
onset and
and degree
degree of
degree of shear
of shear thickening
shear thickening is
thickening is extremely
is extremely high.
extremely high. The
high. maximum RF
The maximum
maximum RF value
value of of
presheared solution at Q = 110 m/day
m/day was
was 26.6
26.6 which
which is
is more
more
presheared solution at Q = 110 m/day was 26.6 which is more than 6 times lower than that of than
than 6
6 times lower than that of
prefiltered
prefiltered solution
solution at comparable
at comparable velocity.
velocity.Additionally,
Additionally, RRF of
RRF presheared
prefiltered solution at comparable velocity. Additionally, RRF of presheared solution at Q = 110of solution
presheared at
solutionQ = 110
at Qcc/min
= 110
was reduced
cc/min
cc/min was to 1.7 compared
was reduced
reduced to 1.7
to to 1.8 andto
1.7 compared
compared to2.2
1.8for
1.8 and
andpresheared
2.2 for
2.2 solution atsolution
for presheared
presheared Q = 15 cc/min
solution at Q
at Q == and prefiltered
15 cc/min
15 cc/min and
and
solution
prefilteredat Q = 0.5
solution cc/min,
at Q = respectively.
0.5 cc/min,
prefiltered solution at Q = 0.5 cc/min, respectively. respectively.

Figure 11. Resistance factor versus interstitial velocity for polymer B presheared at different flow rates.
Figure 11
Figure 11 Resistance
Resistance factor
factor versus
versus interstitial
interstitial velocity
velocity for
for polymer
polymer B
B presheared
presheared at
at different
different flow
flow rates.
rates.

3.4. Permeability
3.4. Permeability Reduction
Reduction
Energies 2018,12,
Energies 2019, 11,49
x FOR PEER REVIEW 18
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25

Polymer retention in porous media has similar importance to its viscoelasticity (discussed
3.4. Permeability Reduction
above) on the sweep efficiency and injectivity. It is a determining parameter in screening EOR
Polymer
polymers. retention
When HPAM inisporous media in
transported has similarmedia,
porous importance
it tends totoitsadsorb
viscoelasticity
on rock (discussed
surfaces and above)
may
on
trapthewithin
sweep small
efficiencyporesandresulting
injectivity.
in Itpolymer
is a determining
retention.parameter
Polymer in screeningreflects
retention EOR polymers.
different
When HPAM such
mechanisms is transported in porous
as adsorption, media,(mechanical
straining it tends to adsorb on rock and
entrapment) surfaces and may trap
hydrodynamic within
retention
small
(rate pores
effect)resulting
[72,83]. in Aspolymer retention.ofPolymer
a consequence polymerretention
retention, reflects different mechanisms
permeability reduction occurs. such
as adsorption, straining (mechanical entrapment) and hydrodynamic
Experimentally, permeability reduction can be evaluated by residual resistance factor (RRF) [57].retention (rate effect) [72,83].
As a consequence
RRF is a measure of polymer
of theretention,
extent ofpermeability
permeability reduction
reduction occurs. Experimentally,
of porous media duepermeability
to polymer
reduction can be
injection. RRF evaluated
correlates by residual
directly with theresistance factorof(RRF)
permeability [57]. media and the molecular weight
the porous
RRF is a Therefore,
of polymer. measure of higher
the extent RRFof values
permeability reduction
may result fromofpolymer
porous media due in
flooding to polymer injection.
low permeability
RRF correlates
reservoirs directly
using with the permeability
high molecular of the porous
weight polymers. mediafor
Generally, and the molecularporous
homogeneous weightmedia
of polymer.
with
Therefore, higher
lower contrast RRF values may
in permeability result from
of different zonespolymer flooding
or layers, in low permeability
the intention reservoirs
is to obtain lower using
RRF values
high
(RRFmolecular
≤ 2) whileweight
keepingpolymers.
RF valuesGenerally, for homogeneous
higher possible at reservoir porous
velocitiesmedia
[84].with
This lower contrastthe
is to increase in
permeability of different
sweep efficiency zones flooding
of polymer or layers, process
the intention is to obtain
by reducing the lower RRFratio
mobility values of(RRF ≤ 2) while
displacing and
keeping
displaced RF fluids.
values higher
However, possible at reservoir
higher RRF valuesvelocities
can [84]. This is to increase
be beneficial where the the sweep
porous efficiency
media of is
polymer flooding
heterogeneous withprocess by reducing
significant contrastthe
inmobility
permeabilityratio of displacing and displaced
different layers. fluids.higher
In such cases, However,RRF
higher
values RRF
couldvalues
resultcan in be beneficial
better where the
conformance porous
control andmedia is heterogeneous
thereby improved sweep with significant contrast
efficiency through
in permeability of different layers.
flow diversion into un-swept regions. In such cases, higher RRF values could result in better conformance
control and thereby
Figure 12 depicts improved sweep efficiency
RRF values measuredthrough flow diversion
for prefiltered polymers intoA,un-swept
B and regions.
C at different
Figure 12 depicts
concentrations. It can beRRF seenvalues measured for
that concentrated prefiltered
polymers havepolymers
higher RRF A, compared
B and C at different
to solutions
concentrations. It can be seen
with lower concentration. that concentrated
Furthermore, RRF appears polymers
to be have higher RRF
significantly compared
dependent to solutions
on polymer Mw
with
to a lower
greaterconcentration. Furthermore, RRF
extent than concentration. This appears
could betoelucidated
be significantly dependent
by looking at a on polymer
similar Mw
polymer
to a greater extent
concentration of 1000 than
ppm,concentration.
we can see RRF This
forcould
polymers be elucidated
A, B and C by looking
were 1.6, 2.2atand
a similar polymer
9.3 respectively.
concentration
This emphasizes of 1000 ppm, weofcan
the increase RRFseewith
RRFMw for polymers
[79]. A, B and C were 1.6, 2.2 and 9.3 respectively.
This emphasizes the increase of RRF with Mw [79].

(a) (b)
Figure 12.
Figure 12 Residual
Residual resistance
resistance factor
factor (RRF)
(RRF) of
of prefiltered
prefiltered polymers A, B
polymers A, B and
and C.
C. (a)
(a) Semi-dilute polymer
Semi-dilute polymer
solutions; (b)
solutions; (b) Concentrated
Concentrated polymer
polymer solutions.
solutions.

Figure
Figure 13
13 displays
displays the impact of
the impact of polymer
polymer pretreatment
pretreatment (prefiltering,
(prefiltering, reinjecting
reinjecting and
and preshearing)
preshearing)
on RRF values. Presented RRF values are quite scattered. This could be
on RRF values. Presented RRF values are quite scattered. This could be due to challengesdue to challenges on measuring on
‘true’ RRF which
measuring ‘true’ has
RRFbeen
which debated in the
has been literature
debated [84].literature
in the One reason[84].could be due could
One reason to experimental
be due to
artifacts ascribed
experimental to the
artifacts amount
ascribed of brine
to the amount andofstrategies
brine and applied
strategiesduring
appliedbrine post-flush
during such as
brine post-flush
tapering [67]. Another reason could be due to unapproachable steady-state
such as tapering [67]. Another reason could be due to unapproachable steady-state condition duringcondition during the
injection of brine
the injection alonealone
of brine after polymer flooding
after polymer to satisfy
flooding Darcy’sDarcy’s
to satisfy Law conditions in Equation
Law conditions (2). This is
in Eq.2. is
suggested
suggested due to the viscoelasticity of retained molecules
to the viscoelasticity of retained molecules [85]. [85]. However, in some cases, the impact
in some cases, the impact
of
of mechanical
mechanical degradation
degradation on RRF RRF waswas not
not significant.
significant. This might be due to the the reason
reason that
that high
high
molecular
molecular species
species tend to to adsorb
adsorb first
first as
as the
the polymer
polymer transports
transports in in porous
porous media.
media. High
High molecular
molecular
species could also be found in degraded solutions if degradation is not significant which may be
Energies 2019, 12, 49 19 of 25

Energies 2018, 11, x FOR PEER REVIEW 19 of 25

species could also be found in degraded solutions if degradation is not significant which may be
enough to
enough to form
form aa similar
similar adsorbed
adsorbed layer
layer of
of non-degraded
non-degraded solutions
solutions [70].
[70]. Measuring
Measuring ‘true’ RRF is
'true' RRF is an
an
essential task
essential task that
that would
would certainly
certainly improve
improve thethe estimation
estimation of
of effective
effective polymer
polymer viscosity
viscosity in
in porous
porous
media by using the term RF⁄RRF.
media by using the term RF/RRF.
However, the
However, the general
general trend
trend from
from the
the data
data presented in Figure
presented in Figure 1313 shows that pretreatment
shows that pretreatment of of
polymer solutions
polymer solutionsprior
priortotoinjection
injectioninto
into
thethe porous
porous media
media results
results in a in a reduction
reduction in RRFin values.
RRF values.
That
That is, RRF values of prefiltered solutions are generally higher than RRF of presheared
is, RRF values of prefiltered solutions are generally higher than RRF of presheared and reinjected and
reinjected solutions.
solutions.

Figure 13. Residual resistance factor (RRF) of polymers A, B and C at different concentrations.
Figure 13 Residual resistance factor (RRF) of polymers A, B and C at different concentrations.
3.5. Polymer Injectivity
3.5. Polymer Injectivity
As stated before, polymer injectivity is a measure of how efficiently polymer solution can be
As
delivered stated before, polymer
into reservoir matrix. injectivity
The shear is a measure
viscosity of how efficiently
measurement polymer
alone cannot solution
predict can be
injectability
delivered
of polymer solutions, as it does not reflect the existence of all flow regimes during polymer flow of
into reservoir matrix. The shear viscosity measurement alone cannot predict injectability in
polymer solutions,
porous media. as it other
Besides does not reflect
factors, the existence
matrix fracturingofisall
oneflow regimes
major concernduring polymerflooding
in polymer flow in
porous
projectsmedia. Besidespolymer
that restricts other factors, matrix
injection. fracturing
Injection underis one major
matrix concernthat
condition in polymer
may evolve flooding
into
projects that restricts
fracture formation polymer
is only injection.
a function Injection
of injection underirrespective
pressure, matrix condition
of polymer thatbulk
mayviscosity
evolve into[86].
fracture
This meansformation
fractureisinitiation
only a function of injectiontopressure,
is more attributed irrespective of particularly
polymer viscoelasticity, polymer bulk viscosity
shear [86].
thickening
This means
behavior thatfracture initiation pressure
yields significant is more build-up.
attributedTherefore,
to polymer viscoelasticity,
polymer injectivityparticularly
could be inferredshear
thickening
from RF and behavior that yields significant
RRF measurements. pressuregradient
The pressure build-up. Therefore,
associated polymer
with high injectivity
RF values couldthat arebe
inferred from RF and RRF measurements. The pressure gradient associated with
found at wellbore region reduces polymer injectivity. Additionally, the decline in polymer injectivity high RF values that
are
mightfound
occur at when
wellbore regionisreduces
retention high as polymer
reflected injectivity.
by high RRF Additionally,
in this study the(e.g.,
decline
RRFin> polymer
3 is not
injectivity
recommended might occur
for EORwhen retention Shear
applications). is highthickening
as reflected by high
may RRF in this
be dampened forstudy
each (e.g.,
polymerRRFeither
> 3 is
not recommended for EOR applications). Shear thickening may be dampened
by increasing the polymer concentration or mechanically degrading the polymer solution before the for each polymer either
by increasing
injection. From the polymer concentration
economical perspective, the or mechanically
former requires degrading
increasingthethe
polymer
dosagesolution
of polymer before the
which
injection.
subsequentlyFrom economical
demands highperspective,
cost. It maythe alsoformer
yield inrequires increasing
high RRF. Whereas the dosage
the of polymer
latter relates which
to polymer
subsequently demandspolymer
type more specifically high cost. MwIt may also yield
at which in high
the cost RRF.
of the Whereas the process
manufacturing latter relates
of low toand
polymer
high
type more specifically
Mw polymer polymer
is quite similar [87].Mw Theatloss
which the cost
of shear of the within
viscosity manufacturing
20–30% due process of low andcould
to preshearing high
Mw polymereconomically
be tolerated is quite similar and[87]. Thealoss
cause of shearreduction
significant viscosity within 20-30% due
in extensional to preshearing
viscosity that results could
in a
be tolerated economically and cause a significant reduction in extensional viscosity
reduction of resistance factor [71]. Additionally, preshearing could also be beneficial, so that high that results in a
reduction of resistance
molecular species factorand
are sheared [71].avoided.
Additionally, preshearing
These species couldresponsible
are mainly also be beneficial,
for wellbore so that high
plugging
molecular species are sheared and avoided. These species are mainly responsible
problems that result in permeability reduction. This may increase the shear rates at wellbore area that for wellbore
plugging
promotes problems that result
pressure build-up andin eventually
permeability reduction. This
mechanically maythe
degrade increase
polymer the solution.
shear rates Thisat wellbore
suggests
area that promotes pressure build-up and eventually mechanically degrade the polymer solution.
This suggests preshearing high Mw polymer solution is a favorable strategy to optimize its injectivity
which is consistent with other studies [88].
Energies 2019, 12, 49 20 of 25

preshearing high Mw polymer solution is a favorable strategy to optimize its injectivity which is
consistent with other studies [88].

4. Conclusions
Series of core flood experiments have been performed to investigate in-situ behavior of partially
hydrolyzed polyacrylamide polymers (HPAM) in porous media. The influence of HPAM molecular
weight and concentration on polymer in-situ rheology has been investigated. Additionally, the impact
of mechanical degradation on polymer rheological behavior has been studied. Based on the results,
polymer injectivity can be optimized. More specifically, the following conclusions could be made:

• In-situ rheological behavior of HPAM in porous media is different from bulk rheology observed
in the rheometer.

- Shear thickening behavior was observed at high velocities representative of those present
in the near wellbore region. Near-Newtonian behavior was observed at low velocities
representative of those present deep in the reservoir.
- The degree and magnitude of shear thickening increased for higher polymer Mw
and concentration.
- Shear thinning behavior at low velocities was observed for concentrated solutions while
not for semi-dilute solutions.

• Exposing HPAM solutions to mechanical degradation through preshearing process prior to

injection facilitates its flow in porous media and enhances its injectivity. This is ascribed to a
reduction in viscoelastic properties.

- Onset of shear thickening shifted to higher velocities.

- The magnitude and the degree of shear thickening behavior were reduced while in-situ
viscosity at low flow rates was maintained.

• RRF appears to be dominated by molecular weight and concentration.

- High RRF found for high molecular weight polymers with high concentration.
- Degraded solutions have lower RRF values specifically for concentrated solutions of high
Mw polymers. This effect was more pronounced when polymer solution was degraded at
very high velocities.

• Improvement (reduction) in polymer viscoelastic properties and RRF through preshearing process
can optimize polymer injectivity.

Author Contributions: Conceptualization, T.S. and A.S.; Formal analysis, B.A.-S., T.S., B.S.S. and A.S.;
Investigation, B.A.-S.; Methodology, B.A.-S., and B.S.S.; Project administration, A.S.; Supervision, T.S., B.S.S. and
A.S.; Writing—original draft, B.A.-S.; Writing—review & editing, T.S., B.S.S. and A.S.
Funding: This research received no external funding.
Acknowledgments: We wish to thank Energi Simulation, Canada and the PETROMAKS 2 program at Norwegian
Research Council for financial support. We also acknowledge Petroleum Development Oman (PDO) for providing
study scholarship for Badar Al-Shakry.
Conflicts of Interest: The authors declare no conflict of interest.
Energies 2019, 12, 49 21 of 25

Nomenclature
A = core cross-sectional area (cm2 )
AF4 = Asymmetrical flow field-flow fractionation
ASP = Alkaline Surfactant Polymer
C = concentration (ppm)
C∗ = critical overlap concentration (ppm)
D = core dimeter (cm)
Deg = mechanical degradation (%)
EOR = enhanced oil recovery
GPC = gel permeation chromatography
HPAM = partially hydrolyzed polyacrylamide
K = flow consistency index (cP.s(n−1) )
Kabs = absolute permeability (Darcy)
Kwf = absolute permeability after polymer flow (Darcy)
Kwi = absolute permeability before polymer flow (Darcy)
L = core length (cm)
LSP = Low Salinity Polymer
Mw = molecular weight (MDa)
MWD = molecular weight distribution, dimensionless
n = flow behavior index, dimensionless
PV = pore volume, dimensionless
Q = injection flow rate (cc/min)
R2 = coefficient of determination, dimensionless
RF = resistance factor, dimensionless
RRF = residual resistance factor, dimensionless
SAOS = small-amplitude oscillatory shear
SEC = size exclusion chromatography
TDS = total dissolved solids
v = interstitial velocity (m/day)
vc = onset of shear thickening (m/day)
vD = Darcy or Superficial velocity (m/day)
∆Pp = pressure drop during polymer flow (bar)
∆Pw = pressure drop during water flow (bar)
ηe = effluent viscosity (cP)
ηi = injected solution viscosity(cP)
ηw = brine viscosity (cP)
φ = porosity, dimensionless
.
γ = shear rate (s−1 )

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